Method of producing gas



Jan. 19, 1937; T `MGEL 2,067,940

METHOD OF'PRODUGING GAS Filed Nov. 16, 1933 f Patentedv Jan. 19, 1937 My invention relates to a process for making rrEo STATES,

v 2,067,940 l 4 METHOD 0F PRODUCING GAS Y Theodore Nagel,

Delaware Brooklyn, N. Y., assigner to Carburetted Gas, Ine.,

a. corporation of hydrocarbon'flxed gases from oil or hydrocarbon vapors and provides the maximum yield of a method 'for obtaining non-condensible hydro- 5 carbons or fixed gases with a minimum yield -of condensate.

. A return of .ered good practice converting oil hydrocarbons into whereas my invention provides a methods for fixed gases,

`20% to 30%' condensate is considwith present commercial method wherein the condensate yield is reduced to not substantially more than 10% by weight of the hydrocarbons charged.

It is well recognized that for heating a versely as its volume, i. e.

the time required unit weight of matter varies indirectly-as its density;

is exceedingly greater than the volume of the equivalent weight of liquid hydrocarbons.

By heat intensity oil can be converted from a. liquid tovapor and finally to gas. jected to a pressure around 200 pounds per square inch or higher pressures, oil can be heatedto within a temperature 700 F. to approximately ing the oil as range of approximately 900 F. while maintaina liquid. On releaseof the pressure, by injecting the hot oil into a heat insulated chamber, for' example, the liquid flashes. almost instantly into vapor and gas with a temperature drop in the order of 50 F. This'is an endothermic action. On cooling, the major porfixed gases.

' tion of the mixture will condense, only a minor portion remaining as hydrocarbon permanent or 0d If. on the other hand, instead of mer-ely in- .iectlng the hot-oil into a ber, the heated oil into a hot zone in vaporl gas mixture perature range of approximately 1200" F. to ap' proximatelyf1600 F.,

while on cooling the proportion -of condensate to hydrocarbon heat insulated chamunder pressure be released hich the temperature of the is raised to within a temvfor example, I find that xed gases produced has been decreased; nevertheless the condensible gases will still amount to from 20% to 30% by weight of the original charge.

of the results This is far ln excess obtained by my pr'cess.

I have found by extensive research into the pyrolysls of hydrocarbons,

i.A e., dissociation and reactions of the hydrocarbons produced by the application of heat, within the temperature range- 1600" F., that the complex hydro- Athere is a uniting of lower When sub- In the pyrolysis of `hydrocarbons thesereactions 10- are known as polymerizing. In other words, molecular weight reagents to forni-complex hydrocarbons of higher molecular weights-polymerization products that are condensible. 15

I propose, therefore, by the method of my in#- vention to control the primary dlssociations and secondary reactions. above referredto by controlling the heating and ,cooling so that overlapping ofthe periods :for primary andsecondary reactions is reduced to a minimum, thereby converting substantially all thefoil to substantially all nonpcondensible hydrocarbon gases, with the yield of condensate reduced to around 10% or less by weight of the original hydrocarbons charged as compared with from two to three times this quantity of condensate yield from commercial operating practices prior to my invention. In other words, the presentinvention provides for regulating the yield of hydrocarbon fixed gases from oil or from hydrocarbon' vapors by control of the heating and cooling so that the maximum yield of hydrocarbon fixed gases is attained with minimum yield of condensate as-compared with the 20% toV 30% condensate. yield ofjprior meth- Figs. 1 and 2 of the accompanying drawing.-

illustrate diagrammatically embodiments of my invention.

As a practical example of my improved method,

the following procedure may be followed:

Oil subjected to superatmospherlc pressure o not less than 150 pounds pressure to the square inch is heated in any suitable fashion to a vaporizing .temperature ranging approximately from 700 F.to 900 F. under conditions to maintain the oil as a liquid. If the pressure on this heated oil be released by injecting the oil into a heat insulated chamber it-will instantly flash into a vapor gas mixture with a temperature drop of say F. I'propose, however, to release the pressure on the hot oil by injecting the oil as shown at I in. Fig. 1 into a hot zone such as chamber 2 which, by supplying hot lean gas thereto as shown at 3. is at such a temperature thatthe vapor gas in character, can take place 'to a substantial" amount, I cool the gas formed on the heating cycle to below 1000 F., by adding cool carburetted gasthereto as indicated at 4 with the result that not more than, of the original amount of hydrocarbons charged reverts to a condensate, as compared with the relatively high yield of 20% to 30% condensate obtained in the practice of priory methods. l

It will be appreciated, therefore, that as so far l described my improved method provides for producing hydrocarbon fixed gases from oil by heating the oil under controlled temperature and presv sure vconditions whereby the oil will be maintained a liquid, the pressure on the heated oil being released by injecting the oil into a hot zone to be converted almost instantly into gas land the complex hydrocarbons decomposed into the more simple aliphatic lower molecular weight vgaseous hydrocarbons, cooling being thereafter immediately eilectedA before asubstantial portion..of the oleiins of the primary. decomposition products recombine, thereby providing a method involving controlled heating and cooling for ob-A I have found thatl the principal polymerizing reagents entering into the secondary reactions, which I avoid as far as practicable by rapid heating and cooling, are mostly the highly unsatu' rated hydrocarbons of the primary dissociation products, which as `I have already mentioned' come under the classification of theolefinic portions of the primary decomposition products. I may take advantage of this condition, therefore, by effecting primary dissociation in ahot zone in the presence of hydrogen to effect partial saturation of the highly unsaturated hydrocarbons; thereby reducing the polymerizing reagents and to the extent further decreasing the yield of condensate. v

lIt will Vbe appreciated ofcourse that 'the hydrogen'maybe supplied from'a'ny suitable source. For example,` from carbon monoxide hydrogen gas in connection with'the making of a carburetted carbon monoxide hydrogen gas mixture.

In the making of such gas mixture the leaner gas, i. e., the uncarburetted carbon monoxide hydrogen gas mixture can be produced by any desired process, such as the continuous flow prpcessof my copending application Serial No. 653,619, flied January 26, 1933. Oil ,heated under pressure as above described is then injected into this leaner gas, as indicated at 5.inFig. 2 thel leaner gas I being at sufliciently high temperature to provide the sensible and latent .heat requirements for in- The enriched or carburetted carbon monoxide hydrogen gas mixture thus produced is immediately thereafter rapidly cooled to the temperature range where polymerization cannot take place, thereby retarding am avoiding to a lub stantial amount the secondary reactions throughout the heating and cooling.

Rapid vcooling may be effected in any practicable manner, as for example by passing the hot carburetted 'gas in countercurrent flow 5 through the heater for the oil, for heat recuperation, to supply the heat deficiency of the lean gas; or gas cooling may be effected by passing the hot carburetted gas through a waste heat boi1er;'or -water spray may be injected into the hot gas. prefer, however, to inject cooled carbon monoxide hydrogen gas or cooled-carburetted carbon monoxide hydrogen gas into the hot hydrocarbon fixed-gases as shown 'at- 6 in Fig. 2 i-n suiiicient@ volume to instantly cool the hot gas by contact to below 1000 F., cooling to room temperature being effected thereafter by any suitable means.

The time consumed in heating and cooling after hashing the hot liquid oil into a vapor gas mixture may be variedl but should not exceed six seconds.

-When the higher temperatures are employed the time may not exceed one second or even less.

This variation in time will be appreciated when it' is understood that dissociation and polymerizv ing reactions take place with increasing rapidity with increase in temperature. Consequently the higher the temperature employed within the specified limits, the shorter will be the period for heating and cooling in order to prevent the slower polymerizing reactionsoccurring to a substantial amount before substantial completion of the more rapid primary dissociation on heating and to retard or avoid polymerizing reactions during cooling, so that little or substantially no polymerization occurs during the period of heating and cool-f ing, namely, before the gas has been cooled to a te perature where polymerizing reactions do not .o cur.

From all the foregoing, therefore, it will be appreciated that I have provided a process for gen- 40 erating hydrocarbon xed gases in which a vaporgals mixture is heated almost instantly to atemperature at which practically all .the more complex 'hydrocarbons are converted into primary dissociation products;V the gas mixture immediately after attaining the desired high temperature being rapidly cooled to retard or avoid a substantial amount of secondary or polymerizing reactions, whereby through this controlled heating and cooling thel yield of hydrocarbon fixed gases is regulated enabling the maximum yield of hydrocarbon fixedgases to be obtained with a minimum yield of condensate.

In addition to the advantages accruing to my V invention by reason of the fact that I can regulate the yield of hydrocarbon fixed gases from oil by control ofthe heating and cooling so as to obtain the maximum yield of hydrocarbon fixed gases and theminimumyield of condensate as distinguished Vfrom the 20% tia-30% condensate 60 heretofore considered. good practice, my invention possesses anotherand very material advantage.

It is well known that unrecycled or straight run heavy oils, for example A. P; I. 16 to 20 ZB.

oils free of 4moisture arid refinery residues, have 65 higher heating values, namely, higher B. t. u. value of the hydrocarbon content per gallon than gas oils, such for example as A. P. I. 36 to 40 B. oils currently used for gas carburetion. These heavier oils `contain, heavier hydrocarbons, boil- A ing at higher temperatures than the hydrocarbons of gas oils.

By employing the heavier oils in the practice of my invention in place of gas oils and controlling the heating and cooling as above set out, it 'will 75 aoeaeao ifi! be appreciated that more desirable gaseous carburants can be generated from these heavier oils than from the gas oils because the heavier oils yield larger quantities of olei'lns, which are more desirable carburants for gas enrichment than gaseous paraiins.

Under present methods of carburetting no control is maintained to prevent polymerization of the Olens, with the result that the heavier oils yield more drip oil and tar condensate than the gas oils.

With my invention, however, the yield of condensate from the heavier oils maybe kept to as low as 10%, thereby enabling the lower cost heavier oils to be used for carbureting withvthe advantage of yielding a more desirable gaseous carburant. Y

Throughout the foregoing and in the appended claims the expression hydrocarbon non-condensible,permanent or fixed gases is to be interpreted to mean the hydrocarbons that remain as 'gases under the usual temperatures and pressures en countered in public utility gas distribution.

1. The process of generating hydrocarbon iixedV gases from oil, which process comprises supplying substantially the maximum heat to the oil While maintaining substantially all of the oil as a. liquid by preheating the oil to within a temperature range of approximately 700 F. to 900 F. While the oil is subjected to a pressure of at least pounds per square inch, injecting the preheated oil into a hot gaseous medium, the volume and temperature of which are such that the hydrocarbons are approximately instantly heated to a temperature within a temperature range of 1200 F. to 1600 F. substantially instantly to decompose the hydrocarbons to gaseous hydrocarbons the unsaturated hydrocarbons of which arel composed of olens, and before polymerization in excess of 10% takes place contacting the hot gases in direct heat exchange relation with a relatively cool fluid, to cool the gaseous hydrocarbons to belowP polymerizing ti .iperature and excluding polymerization during cooling, thereby -to retain the maximum heating value of the gassubstantially maximum heat to the oil while maintaining substantially all of the oil as a liquid by preheating the oil to within a temperature range of approximately 700 F. to 900? F, while subjected to a pressure not less than 150 pounds per square inch, injecting the preheated oil into a hot gaseous medium, the volume and temperature of which are such that the hydrocarbons are approximately instantly heated to a temperature within a temperature range of 1200 F. to 1600 F. substantially instantly to decompose the hydrocarbons to gaseous hydrocarbons the unsaturated hydrocarbons of which are composed of olefins, and before polymerization in excess of 10% takes place contacting the hot gases in direct heat exchange relation with water to cool the gaseous hydrocarbons to below polymerizingtemperature and excluding polymerization during cooling; thereby to retain the maximum heating value of the gaseous hydrocarbons.

4. The process of generating hydrocarbon fixed gases from oil, which process comprises supplying substantially the maximum heat to the oil* while maintaining substantially all `of the oil as a liquid by preheating the oil to within a temperature range of approximately '700 F. to 900 F. while subjected to a pressure not less than 150 pounds persquareinch,injecting the preheated oil into hot carbon monoxide hydrogen gas, the volurne and temperature of which are such that the hydrocarbons are approximately instantly heated to a temperature within a temperature range of 1200 F. to 1600 F. substantially instantly to decompose the hydrocarbons to gaseous hydrocarbons the unsaturated hydrocarbons of which are composed of olens, and before polymerization in excess of 10% takes place contacting the hot gases in direct heat exchange relation with relatively cool carburetted carbon monoxide hydrogen gas, to cool the gaseous hydrocarbons to below polymerizing temperature, and excluding polymerization during cooling, thereby to retain 5 -v the maximum heating value of the gaseous hydrocarbons.

THEODORE NAGEL. 

